CN1067663A - In some polymkeric substance, prevent crystal formation method - Google Patents
In some polymkeric substance, prevent crystal formation method Download PDFInfo
- Publication number
- CN1067663A CN1067663A CN92104509A CN92104509A CN1067663A CN 1067663 A CN1067663 A CN 1067663A CN 92104509 A CN92104509 A CN 92104509A CN 92104509 A CN92104509 A CN 92104509A CN 1067663 A CN1067663 A CN 1067663A
- Authority
- CN
- China
- Prior art keywords
- polymkeric substance
- mphenylenediamine
- mixture
- mole
- diamino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Polyamides (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Liquid Crystal Substances (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Before-diamide two by some and some two amine mixt react, should two-lactan fusion in advance, with the formation of inhibition crystalline.
Description
In the co-applications and the U.S. Patent application 07/402295 of assigning, disclosed the method for preparing some kind polymeric amide.Generally, this method comprises by a kind of pair-lactan and one or more diamines reacts, and generates this polymkeric substance.Disadvantageously, when using the combination of some diamines or diamines, in the made polymkeric substance crystal is arranged, this can see that it has spherocrystal and obviously comes out by microscopically.With such polymkeric substance compacting film forming is opaque often, and during these moulds of bending, can break.
The invention provides a kind of processing technology, when some polymeric amide of preparation, can suppress crystalline and generate.
The invention provides a kind of improved method prepares by N, N '-isophthaloyl is two-and the mixture of the Ursol D of hexanolactam and mphenylenediamine and 10-50 mole % reacts the polymkeric substance that forms, or with mphenylenediamine and 10-90 mole %4,4 '-mixture of diamino-diphenyl ether reacts the polymkeric substance that forms, or with mphenylenediamine and 0-90 mole %3,4 '-mixture of diamino-diphenyl ether reacts the polymkeric substance that forms.In this improved method, utilize such step to suppress crystalline in the resulting polymers and form: promptly this kind two-mixture of lactan and diamines react before earlier should pair-the lactan fusion.
General step of improving one's methods of the present invention is as follows:
This pair-lactan of solid state is placed reactor, with nitrogen with this still scavenging.Then this still is heated to this pair-lactan fine melt.Under the vigorous stirring situation, add this kind two amine mixt, the reaction-ure mixture that obtains being suitable for then.Then the reaction mixture heating is made each composition reaction, become this polymkeric substance.Generally, this Heating temperature is 220-280 ℃, until reacting completely.
In following example, heat-up time is for continuing about 2.5-4 hour.Under each situation, be transparent by the inventive method products therefrom, and under 100 power microscopes, show less than spherocrystal.Before with it compacting film forming, place methyl alcohol a few hours of heat to remove remaining lactan in the polymkeric substance that as above makes.Then with isolating polymkeric substance in the baking oven inner drying, on a letterweight machine in 300 ℃ of compactings 1 minute, but form the film of transparent bending.Example 4 is case of comparative examples, wherein except that this pair-lactan without pre-fusion promptly with these diamine reactants, all the other are identical with example 1.
Testing method
It is that the sample of this multipolymer is tested in differential scanning calorimeter (DSC) that the glass transition temperature Tg of multipolymer is measured, press the capable described mode of the 4th hurdle 10-25 among the US4501886 of J.P.O ' Brien, difference is to use Du Pont 2100 thermal analyzers, at the Tg of the transformation of about 180-250 ℃ scope note as this copolymer sample.The logarithmic viscosity number (inherent viscosity) that dissolves in the polymkeric substance of appropriate solvent is that it is defined as the measuring of the extent of polymerization of this polymkeric substance routinely:
η
inh=1n(t/t
0)/c
Its measuring method is to use a capillary viscosimeter, in 25 ℃, measures the flushing time of the concentration c solution of this polymkeric substance, and wherein t is the solution flushing time, t
0It is the flushing time of independent solvent.To multipolymer of the present invention, measure logarithmic viscosity number and be to use the 4%(weight of lithium chloride in N,N-DIMETHYLACETAMIDE) solution is as solvent, wherein molten copolymer sample concentration be about 0.5 this multipolymer of gram in per 100 milliliters of these solvents.Illustrate the present invention by following embodiment, but non-limitation of the invention.
Example 1
By 3,4 '-mixture and the N of diamino-diphenyl ether and mphenylenediamine, N '-isophthaloyl is two-the hexanolactam reaction, form polymkeric substance.
The 5.0 gram N that in a Glass tubing, pack into, N '-isophthaloyl is two-hexanolactam.Seal with this effective nitrogen scavenging and by a screw-cap that is lined with tetrafluoroethylene.This pipe placed be preheated to 4 inches high aluminium ingots of 250 ℃.As N wherein, N '-isophthaloyl is two-hexanolactam fusing fully after, in nitrogen atmosphere, add 1.37 gram mphenylenediamines and 0.28 gram 3,4 '-mixture of diamino-diphenyl ether.Shake this pipe thing is mixed, send back to then in this aluminium ingot and stopped 2.5 hours.
Formed polymkeric substance is transparent, observes with 100 power microscopes, does not see spherocrystal.A part of polymkeric substance is placed on a few hours in the hot methyl alcohol, to remove remaining lactan.Isolated polymkeric substance is dry in baking oven, in 300 ℃ of compactings 1 minute in the letterweight machine, obtain diaphragm transparent and can bending.
Example 2
By the mixture and the N of mphenylenediamine and Ursol D, N '-isophthaloyl is two-the hexanolactam reaction, form polymkeric substance.
Press the same way as of example 1, difference is to use the mixture of 1.06 gram mphenylenediamines and 0.46 gram Ursol D to replace the hybrid diamine of former usefulness.The mixture heating up time is 4 hours.
Form transparent polymkeric substance.Microscopically be can't see spherocrystal.The logarithmic viscosity number of resulting polymers is 0.6, and Tg is 196 ℃.
Example 3
By mphenylenediamine and 4,4 '-mixture and the N of diamino-diphenyl ether, N '-isophthaloyl is two-the hexanolactam reaction, forms polymkeric substance.
Press the same way as of example 1, difference be to use 0.46 gram mphenylenediamine and 1.97 grams 4,4 '-mixture of diamino-diphenyl ether replaces the mixed amine of former usefulness.The mixture heating up time is 4 hours.Obtain transparent polymkeric substance.Microscopically be can't see spherocrystal.The logarithmic viscosity number of resulting polymers is 0.6, and Tg is 190 ℃.
Example 4
Reference examples is used the reaction mass identical with example 1.
In Glass tubing, adding 5.0 gram N, N '-isophthaloyl is two-hexanolactam, 1.37 gram mphenylenediamines, 0.28 gram 3,4 '-diamino-diphenyl ether., seal with the screw-cap that is lined with tetrafluoroethylene again the Glass tubing scavenging with nitrogen.In room temperature this pipe is inserted in 4 inches high aluminium ingots.With about 2 hours this aluminium ingot is heated to 250 ℃.When fusing takes place, pipe is jolted.This mixture was kept 2.5 hours in 250 ℃.
The polymkeric substance that forms is opaque.Observe down in 100 power microscopes, spread all over spherocrystal in the polymkeric substance.With the methyl alcohol a few hours that a part of polymkeric substance places heat, remove remaining lactan.Isolated polymkeric substance is dry in baking oven, suppressed 1 minute in the letterweight machine in 300 ℃.Form opaque film, this film fractures when bending.
Claims (4)
1, by N, N '-isophthaloyl is two-mixture of the Ursol D of caprolactam and mphenylenediamine and 10-50 mole % or with 4 of mphenylenediamine and 10-90 mole %, 4 '-mixture of diamino-phenyl diphenyl ether or with 3 of mphenylenediamine and 10-90 mole %, 4 '-mixture of diamino-diphenyl ether carries out the improvement of the method for prepared in reaction polymkeric substance, its improvements are, mix with this two amine mixt and heat at this pair-lactan with before reacting, earlier should two-lactan heating and melting, form crystal in the resulting polymers to be suppressed at.
2, the process of claim 1 wherein that two used amine mixt are Ursol D of mphenylenediamine and 10-50 mole %.
3, the process of claim 1 wherein that two used amine mixt are 4,4 of mphenylenediamine and 10-90 mole % '-diamino-diphenyl ether.
4, the process of claim 1 wherein that two used amine mixt are 3,4 of mphenylenediamine and 10-90 mole % '-diamino-diphenyl ether.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/711,967 US5140096A (en) | 1991-06-07 | 1991-06-07 | Polymer preparation from diacylbis-lactam to avoid crystal formation |
US711,967 | 1991-06-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1067663A true CN1067663A (en) | 1993-01-06 |
CN1033095C CN1033095C (en) | 1996-10-23 |
Family
ID=24860234
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN92104509A Expired - Fee Related CN1033095C (en) | 1991-06-07 | 1992-06-06 | Avoidance of crystal formation in certain polymers |
Country Status (9)
Country | Link |
---|---|
US (1) | US5140096A (en) |
EP (1) | EP0587793B1 (en) |
JP (2) | JP3138537B2 (en) |
CN (1) | CN1033095C (en) |
AU (1) | AU2161092A (en) |
CA (1) | CA2109631C (en) |
DE (1) | DE69212477T2 (en) |
RU (1) | RU2083600C1 (en) |
WO (1) | WO1992021710A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09133629A (en) | 1995-11-08 | 1997-05-20 | Kdk Corp | Treatment method for spectrum in spectral measurement and determination method using it |
US9127126B2 (en) | 2012-04-30 | 2015-09-08 | Brewer Science Inc. | Development of high-viscosity bonding layer through in-situ polymer chain extension |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3862262A (en) * | 1973-12-10 | 1975-01-21 | Monsanto Co | Lactam-polyol-acyl polyactam terpolymers |
DE68919804T2 (en) * | 1988-10-14 | 1995-05-24 | Du Pont | Thermoplastic aromatic polyamides. |
-
1991
- 1991-06-07 US US07/711,967 patent/US5140096A/en not_active Expired - Lifetime
-
1992
- 1992-05-25 RU SU925011627A patent/RU2083600C1/en not_active IP Right Cessation
- 1992-06-02 JP JP04165508A patent/JP3138537B2/en not_active Expired - Fee Related
- 1992-06-06 CN CN92104509A patent/CN1033095C/en not_active Expired - Fee Related
- 1992-06-08 CA CA002109631A patent/CA2109631C/en not_active Expired - Fee Related
- 1992-06-08 WO PCT/US1992/004571 patent/WO1992021710A1/en active IP Right Grant
- 1992-06-08 AU AU21610/92A patent/AU2161092A/en not_active Abandoned
- 1992-06-08 DE DE69212477T patent/DE69212477T2/en not_active Expired - Fee Related
- 1992-06-08 JP JP5500598A patent/JPH06508385A/en active Pending
- 1992-06-08 EP EP92913967A patent/EP0587793B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH06107785A (en) | 1994-04-19 |
JPH06508385A (en) | 1994-09-22 |
EP0587793A1 (en) | 1994-03-23 |
CN1033095C (en) | 1996-10-23 |
CA2109631A1 (en) | 1992-12-10 |
RU2083600C1 (en) | 1997-07-10 |
US5140096A (en) | 1992-08-18 |
CA2109631C (en) | 2002-09-17 |
DE69212477D1 (en) | 1996-08-29 |
EP0587793B1 (en) | 1996-07-24 |
AU2161092A (en) | 1993-01-08 |
DE69212477T2 (en) | 1997-01-02 |
JP3138537B2 (en) | 2001-02-26 |
WO1992021710A1 (en) | 1992-12-10 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
OR01 | Other related matters | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 19961023 |